WO2023137791A1 - Waterproof gas-permeable tpu hot-melt adhesive film and preparation process therefor - Google Patents

Waterproof gas-permeable tpu hot-melt adhesive film and preparation process therefor Download PDF

Info

Publication number
WO2023137791A1
WO2023137791A1 PCT/CN2022/074643 CN2022074643W WO2023137791A1 WO 2023137791 A1 WO2023137791 A1 WO 2023137791A1 CN 2022074643 W CN2022074643 W CN 2022074643W WO 2023137791 A1 WO2023137791 A1 WO 2023137791A1
Authority
WO
WIPO (PCT)
Prior art keywords
melt adhesive
adhesive film
waterproof
tpu hot
breathable
Prior art date
Application number
PCT/CN2022/074643
Other languages
French (fr)
Chinese (zh)
Inventor
宾家荃
宾家齐
Original Assignee
广东汇齐新材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东汇齐新材料有限公司 filed Critical 广东汇齐新材料有限公司
Publication of WO2023137791A1 publication Critical patent/WO2023137791A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C

Definitions

  • the invention relates to the field of TPU hot-melt adhesive films, in particular to a waterproof and breathable TPU hot-melt adhesive film and a preparation process thereof.
  • Waterproof and breathable materials have achieved rapid development in the past ten years, and have been widely used in outdoor clothing, architectural decoration, water operations and other fields.
  • waterproof and breathable membrane materials are mainly divided into polyester films and polyether films, both of which have good waterproof performance.
  • polyester films have a large gap compared with polyether films.
  • the present invention provides a waterproof and breathable TPU hot melt adhesive film with good use effect and excellent performance.
  • the invention also provides a preparation process of a waterproof and breathable TPU hot-melt adhesive film, which is simple in preparation and improves the convenience and stability of production and processing.
  • the present invention adopts following technical scheme:
  • a waterproof and breathable TPU hot melt adhesive film comprising the following components in parts by weight:
  • a further improvement to the above technical solution is that the concentration of the solvent is 0.6-0.9 mol/L.
  • a further improvement to the above technical solution is that the concentration of the graphene oxide is 21-25 mg/mL.
  • porogen is at least one of polyvinylpyrrolidone and polyethylene glycol.
  • hydrophobic agent is one or more of polytetrafluoroethylene, polychlorotrifluoroethylene, and polyperfluoroethylene propylene.
  • a further improvement to the above technical solution is that the reducing agent is one or both of glucose and dimethylamine borane.
  • the light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidine) sebacate, poly[[6-[(1,1,3,3-tetramethylbutyl)amine]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidine)imine]-1,6-dihexanediyl[(2,2,6,6-tetramethyl-4- Any one or a mixture of at least two of piperidine) imine]]], bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.
  • a preparation method of a waterproof and breathable TPU hot-melt adhesive film comprising the steps of:
  • step S2 dispersing the porous graphene in step S1 in a solvent, then adding a hydrophobic agent, after reacting for 30 to 60 minutes, adding an appropriate amount of porogen, and stirring evenly to obtain a modified porous graphene dispersion;
  • step S4 Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, add a light stabilizer, stir evenly, and defoam at 0.07 to 0.1 MPa for 35 to 50 minutes. Apply the defoamed mixed solution evenly on the release paper by coating, then send the coated release paper into an oven for drying and drying, and cure the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot melt adhesive film can be obtained.
  • step S4 the coating gap is 0.6-1 mm.
  • step S4 the temperature of the oven is set to 130-150°C.
  • the waterproof and breathable TPU hot-melt adhesive film of the present invention takes into account the moisture permeability and mechanical properties of the film, and also has good tensile strength and excellent waterproof and air permeability; the preparation process is very simple, the energy consumption is low, and the performance of the graphene-containing porous film is easy to control.
  • a waterproof and breathable TPU hot melt adhesive film comprising the following components in parts by weight:
  • the concentration of the solvent is 0.6-0.9 mol/L.
  • the concentration of the graphene oxide is 21-25 mg/mL.
  • the porogen is at least one of polyvinylpyrrolidone and polyethylene glycol.
  • the hydrophobic agent is one or more of polytetrafluoroethylene, polychlorotrifluoroethylene, and polyperfluoroethylene propylene.
  • the reducing agent is one or both of glucose and dimethylamine borane.
  • the light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidine) sebacate, poly[[6-[(1,1,3,3-tetramethylbutyl)amine]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidine)imine]-1,6-dihexanediyl[(2,2,6,6-tetramethyl-4-piperidine)imine] ]], bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, or a mixture of at least two.
  • a preparation method of a waterproof and breathable TPU hot-melt adhesive film comprising the steps of:
  • step S2 dispersing the porous graphene in step S1 in a solvent, then adding a hydrophobic agent, after reacting for 30 to 60 minutes, adding an appropriate amount of porogen, and stirring evenly to obtain a modified porous graphene dispersion;
  • step S4 Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, add a light stabilizer, stir evenly, and defoam at 0.07 to 0.1 MPa for 35 to 50 minutes. Apply the defoamed mixed solution evenly on the release paper by coating, then send the coated release paper into an oven for drying and drying, and cure the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot melt adhesive film can be obtained.
  • the coating gap is 0.6-1 mm.
  • the temperature of the oven is set at 130-150°C.
  • a preparation method of a waterproof and breathable TPU hot-melt adhesive film comprising the steps of:
  • step S4 Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, then add 0.2 parts of light stabilizer, stir evenly, defoam at 0.1 MPa for 40 minutes, evenly coat the degassed mixed solution on the release paper by coating, then send the coated release paper into an oven for drying and drying, and cure the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot-melt adhesive film can be obtained.
  • a preparation method of a waterproof and breathable TPU hot-melt adhesive film comprising the steps of:
  • step S4 Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, then add 0.4 parts of light stabilizer, stir evenly, defoam at 0.07MPa for 35 minutes, evenly coat the degassed mixed solution on the release paper by coating, then send the coated release paper into an oven for drying and drying, and cure the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot melt adhesive film can be obtained.
  • a preparation method of a waterproof and breathable TPU hot-melt adhesive film comprising the steps of:
  • step S4 Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, then add 0.3 parts of light stabilizer, stir evenly, defoam at 0.1 MPa for 45 minutes, evenly coat the degassed mixed solution on the release paper by coating, then send the coated release paper into an oven for drying, and dry the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot-melt adhesive film can be obtained.
  • the raw material composition and parts by weight of this comparative example are as follows: porogen is 0 part;
  • the preparation method is the same as in Example 1.
  • the raw material composition and parts by weight of this comparative example are as follows: graphene oxide and porogen are 0 parts;
  • the preparation method is the same as in Example 2.
  • the TPU films prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to a water vapor transmission rate test, a water pressure resistance test and a tensile strength test.
  • the water vapor transmission rate test adopts the method and performance parameters described in GB/T 1037-1988, and the test results are shown in the following table:

Abstract

Provided are a waterproof gas-permeable TPU hot-melt adhesive film and a preparation process therefor. The waterproof gas-permeable TPU hot-melt adhesive film comprises the following components in parts by weight: 75-90 parts of TPU; 15-40 parts of a solvent; 20-45 parts of graphene oxide; 1-3 parts of a porogen; 0.5-2 parts of a hydrophobic agent; 0.5-1 part of a reducing agent; and 0.1-0.5 parts of a light stabilizer. The waterproof gas-permeable TPU hot-melt adhesive film has a good use effect, has excellent performance, and is easy to prepare, so that the convenience and stability of production and processing are improved.

Description

[根据细则37.2由ISA制定的发明名称]　防水透气TPU热熔胶膜及其制备工艺[Title of the invention formulated by ISA under Rule 37.2] Waterproof and breathable TPU hot-melt adhesive film and its preparation process 技术领域technical field
本发明涉及TPU热熔胶膜领域，特别是涉及一种防水透气TPU热熔胶膜及其制备工艺。The invention relates to the field of TPU hot-melt adhesive films, in particular to a waterproof and breathable TPU hot-melt adhesive film and a preparation process thereof.
背景技术Background technique
防水透气材料在近十年里取得了迅速的发展，在户外服饰、建筑装饰、水上作业等领域得到广泛的应用，在TPU薄膜中，防水透气膜材料主要分为聚酯型薄膜和聚醚型薄膜，都具有良好的防水性能，在透气性能上，聚酯型薄膜相较于聚醚型薄膜，差距效果很大。Waterproof and breathable materials have achieved rapid development in the past ten years, and have been widely used in outdoor clothing, architectural decoration, water operations and other fields. Among TPU films, waterproof and breathable membrane materials are mainly divided into polyester films and polyether films, both of which have good waterproof performance. In terms of breathability, polyester films have a large gap compared with polyether films.
发明内容Contents of the invention
为解决上述技术问题，本发明提供一种使用效果好、性能优异的防水透气TPU热熔胶膜。In order to solve the above technical problems, the present invention provides a waterproof and breathable TPU hot melt adhesive film with good use effect and excellent performance.
本发明还提供一种防水透气TPU热熔胶膜的制备工艺，制备简单，提高生产加工的便利性和稳定性。The invention also provides a preparation process of a waterproof and breathable TPU hot-melt adhesive film, which is simple in preparation and improves the convenience and stability of production and processing.
本发明采用如下技术方案：The present invention adopts following technical scheme:
一种防水透气TPU热熔胶膜，包括如下重量份数的组分：A waterproof and breathable TPU hot melt adhesive film, comprising the following components in parts by weight:
Figure PCTCN2022074643-appb-000001
Figure PCTCN2022074643-appb-000001
对上述技术方案的进一步改进为，所述溶剂的浓度为0.6～0.9mol/L。A further improvement to the above technical solution is that the concentration of the solvent is 0.6-0.9 mol/L.
对上述技术方案的进一步改进为，所述氧化石墨烯的浓度为21～25mg/mL。A further improvement to the above technical solution is that the concentration of the graphene oxide is 21-25 mg/mL.
对上述技术方案的进一步改进为，所述致孔剂为聚乙烯吡咯烷酮、聚乙二醇中的至少一种。A further improvement to the above technical solution is that the porogen is at least one of polyvinylpyrrolidone and polyethylene glycol.
对上述技术方案的进一步改进为，所述疏水剂为聚四氟乙烯、聚三氟氯乙烯、聚全氟乙丙烯中的一种或几种。A further improvement to the above technical solution is that the hydrophobic agent is one or more of polytetrafluoroethylene, polychlorotrifluoroethylene, and polyperfluoroethylene propylene.
对上述技术方案的进一步改进为，所述还原剂为葡萄糖、二甲基胺硼烷中的一种或两种。A further improvement to the above technical solution is that the reducing agent is one or both of glucose and dimethylamine borane.
对上述技术方案的进一步改进为，所述光稳定剂为癸二酸二(2,2,6,6-四甲基-4-哌啶)酯、聚[[6-[(1,1,3,3-四甲基丁基)胺]-1,3,5-三嗪-2,4-二基][(2,2,6,6-四甲基-4-哌啶)亚胺]-1,6-二己二基[(2,2,6,6-四甲基-4-哌啶)亚胺]]]、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯中的任意一种或至少两种的混合物。A further improvement to the above technical solution is that the light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidine) sebacate, poly[[6-[(1,1,3,3-tetramethylbutyl)amine]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidine)imine]-1,6-dihexanediyl[(2,2,6,6-tetramethyl-4- Any one or a mixture of at least two of piperidine) imine]]], bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.
一种防水透气TPU热熔胶膜的制备方法，包括如下步骤：A preparation method of a waterproof and breathable TPU hot-melt adhesive film, comprising the steps of:
S1、将氧化石墨烯分散在水中，然后加入过氧化氢溶液，110～120℃反应1h～8h，反应完成后加入还原剂继续反应3～4h后离心或过滤收集固体产物，得到多孔石墨烯；S1. Disperse graphene oxide in water, then add hydrogen peroxide solution, and react at 110-120°C for 1h-8h. After the reaction is completed, add a reducing agent to continue the reaction for 3-4h, then centrifuge or filter to collect the solid product to obtain porous graphene;
S2、将步骤S1中的多孔石墨烯分散在溶剂中，然后加入疏水剂，反应30～60min后，加入适量的致孔剂，搅拌均匀得到改性多孔石墨烯分散液；S2, dispersing the porous graphene in step S1 in a solvent, then adding a hydrophobic agent, after reacting for 30 to 60 minutes, adding an appropriate amount of porogen, and stirring evenly to obtain a modified porous graphene dispersion;
S3、将TPU置于溶剂中，然后在95～100℃进行搅拌，溶解完全；S3. Put the TPU in the solvent, and then stir at 95-100°C to dissolve completely;
S4、将步骤S2的多孔石墨烯分散液与步骤S3的TPU溶液混合，再加入光稳定剂，搅拌均匀后，在0.07～0.1MPa下脱泡35～50min，将脱泡后的混合溶液通过涂布的方式均匀涂布在离型纸上，然后将涂布后的离型纸送入烘箱中进行烘干干燥，将干燥后的产品常温固化，完全固化后即可得到防水透气TPU热熔胶膜。S4. Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, add a light stabilizer, stir evenly, and defoam at 0.07 to 0.1 MPa for 35 to 50 minutes. Apply the defoamed mixed solution evenly on the release paper by coating, then send the coated release paper into an oven for drying and drying, and cure the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot melt adhesive film can be obtained.
对上述技术方案的进一步改进为，在所述步骤S4中，所述涂布的间隙为0.6-1mm。A further improvement to the above technical solution is that in the step S4, the coating gap is 0.6-1 mm.
对上述技术方案的进一步改进为，在所述步骤S4中，所述烘箱的温度设为130-150℃。A further improvement to the above technical solution is that in the step S4, the temperature of the oven is set to 130-150°C.
本发明的有益效果为：The beneficial effects of the present invention are:
本发明的防水透气TPU热熔胶膜兼顾胶膜的透湿性和力学性能，还具有良好的抗张强度，同时具有优异的防水透气性；制备工艺十分简单，能耗低，含石墨烯的多孔膜的性能易控制。The waterproof and breathable TPU hot-melt adhesive film of the present invention takes into account the moisture permeability and mechanical properties of the film, and also has good tensile strength and excellent waterproof and air permeability; the preparation process is very simple, the energy consumption is low, and the performance of the graphene-containing porous film is easy to control.
具体实施方式Detailed ways
为更好地理解本发明，下面结合实施例对本发明作进一步说明，但是本发明的实施方式不限于此。In order to better understand the present invention, the present invention will be further described below in conjunction with examples, but the embodiments of the present invention are not limited thereto.
一种防水透气TPU热熔胶膜，包括如下重量份数的组分：A waterproof and breathable TPU hot melt adhesive film, comprising the following components in parts by weight:
Figure PCTCN2022074643-appb-000002
Figure PCTCN2022074643-appb-000002
优选地，所述溶剂的浓度为0.6～0.9mol/L。Preferably, the concentration of the solvent is 0.6-0.9 mol/L.
优选地，所述氧化石墨烯的浓度为21～25mg/mL。Preferably, the concentration of the graphene oxide is 21-25 mg/mL.
优选地，所述致孔剂为聚乙烯吡咯烷酮、聚乙二醇中的至少一种。Preferably, the porogen is at least one of polyvinylpyrrolidone and polyethylene glycol.
优选地，所述疏水剂为聚四氟乙烯、聚三氟氯乙烯、聚全氟乙丙烯中的一种或几种。Preferably, the hydrophobic agent is one or more of polytetrafluoroethylene, polychlorotrifluoroethylene, and polyperfluoroethylene propylene.
优选地，所述还原剂为葡萄糖、二甲基胺硼烷中的一种或两种。Preferably, the reducing agent is one or both of glucose and dimethylamine borane.
优选地，所述光稳定剂为癸二酸二(2,2,6,6-四甲基-4-哌啶)酯、聚[[6-[(1,1,3,3-四甲基丁基)胺]-1,3,5-三嗪-2,4-二基][(2,2,6,6-四甲基-4-哌啶)亚胺]-1,6-二己二基[(2,2,6,6-四甲基-4-哌啶)亚胺]]]、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯中的任意一种或至少两种的混合物。Preferably, the light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidine) sebacate, poly[[6-[(1,1,3,3-tetramethylbutyl)amine]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidine)imine]-1,6-dihexanediyl[(2,2,6,6-tetramethyl-4-piperidine)imine] ]], bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, or a mixture of at least two.
一种防水透气TPU热熔胶膜的制备方法，包括如下步骤：A preparation method of a waterproof and breathable TPU hot-melt adhesive film, comprising the steps of:
S1、将氧化石墨烯分散在水中，然后加入过氧化氢溶液，110～120℃反应1h～8h，反应完成后加入还原剂继续反应3～4h后离心或过滤收集固体产物，得到多孔石墨烯；S1. Disperse graphene oxide in water, then add hydrogen peroxide solution, and react at 110-120°C for 1h-8h. After the reaction is completed, add a reducing agent to continue the reaction for 3-4h, then centrifuge or filter to collect the solid product to obtain porous graphene;
S2、将步骤S1中的多孔石墨烯分散在溶剂中，然后加入疏水剂，反应30～60min后，加入适量的致孔剂，搅拌均匀得到改性多孔石墨烯分散液；S2, dispersing the porous graphene in step S1 in a solvent, then adding a hydrophobic agent, after reacting for 30 to 60 minutes, adding an appropriate amount of porogen, and stirring evenly to obtain a modified porous graphene dispersion;
S3、将TPU热熔胶置于溶剂中，然后在95～100℃进行搅拌，溶解完全；S3. Put the TPU hot melt adhesive in a solvent, and then stir at 95-100°C to dissolve completely;
S4、将步骤S2的多孔石墨烯分散液与步骤S3的TPU溶液混合，再加入光稳定剂，搅拌均匀后，在0.07～0.1MPa下脱泡35～50min，将脱泡后的混合溶液通过涂布的方式均匀涂布在离型纸上，然后将涂布后的离型纸送入烘箱中进行烘干干燥，将干燥后的产品常温固化，完全固化后即可得到防水透气TPU热熔胶膜。S4. Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, add a light stabilizer, stir evenly, and defoam at 0.07 to 0.1 MPa for 35 to 50 minutes. Apply the defoamed mixed solution evenly on the release paper by coating, then send the coated release paper into an oven for drying and drying, and cure the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot melt adhesive film can be obtained.
优选地，在所述步骤S4中，所述涂布的间隙为0.6-1mm。Preferably, in the step S4, the coating gap is 0.6-1 mm.
优选地，在所述步骤S4中，所述烘箱的温度设为130-150℃。Preferably, in the step S4, the temperature of the oven is set at 130-150°C.
实施例1Example 1
一种防水透气TPU热熔胶膜的制备方法，包括如下步骤：A preparation method of a waterproof and breathable TPU hot-melt adhesive film, comprising the steps of:
S1、将30份氧化石墨烯分散在水中，然后加入过氧化氢溶液，120℃反应8h，反应完成后加入0.5份还原剂继续反应4h后离心或过滤收集固体产物，得到多孔石墨烯；S1. Disperse 30 parts of graphene oxide in water, then add hydrogen peroxide solution, and react at 120°C for 8 hours. After the reaction is completed, add 0.5 parts of reducing agent to continue the reaction for 4 hours, then centrifuge or filter to collect the solid product to obtain porous graphene;
S2、将步骤S1中的多孔石墨烯分散在溶剂中，然后加入1份疏水剂，反应60min后，加入1.5份致孔剂，搅拌均匀得到改性多孔石墨烯分散液；S2, disperse the porous graphene in the step S1 in the solvent, then add 1 part of hydrophobic agent, after reacting for 60min, add 1.5 parts of porogen, stir to obtain the modified porous graphene dispersion;
S3、将75份TPU热熔胶置于15份酒精溶液中，然后在100℃进行搅拌，溶解完全；S3. Put 75 parts of TPU hot melt adhesive in 15 parts of alcohol solution, and then stir at 100°C to dissolve completely;
S4、将步骤S2的多孔石墨烯分散液与步骤S3的TPU溶液混合，再加入0.2份光稳定剂，搅拌均匀后，在0.1MPa下脱泡40min，将脱泡后的混合溶液通过涂布的方式均匀涂布在离型纸上，然后将涂布后的离型纸送入烘箱中进行烘干干燥，将干燥后的产品常温固化，完全固化后即可得到防水透气TPU热熔胶膜。S4. Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, then add 0.2 parts of light stabilizer, stir evenly, defoam at 0.1 MPa for 40 minutes, evenly coat the degassed mixed solution on the release paper by coating, then send the coated release paper into an oven for drying and drying, and cure the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot-melt adhesive film can be obtained.
实施例2Example 2
一种防水透气TPU热熔胶膜的制备方法，包括如下步骤：A preparation method of a waterproof and breathable TPU hot-melt adhesive film, comprising the steps of:
S1、将35份氧化石墨烯分散在水中，然后加入过氧化氢溶液，110℃反应2h，反应完成后加入0.5份还原剂继续反应3h后离心或过滤收集固体产物，得到多孔石墨烯；S1. Disperse 35 parts of graphene oxide in water, then add hydrogen peroxide solution, and react at 110°C for 2 hours. After the reaction is completed, add 0.5 parts of reducing agent to continue the reaction for 3 hours, then centrifuge or filter to collect the solid product to obtain porous graphene;
S2、将步骤S1中的多孔石墨烯分散在酒精溶液中，然后加入1份疏水剂，反应30min后，加入1份致孔剂，搅拌均匀得到改性多孔石墨烯分散液；S2, disperse the porous graphene in the step S1 in the alcohol solution, then add 1 part of hydrophobic agent, after reacting for 30min, add 1 part of porogen, stir to obtain the modified porous graphene dispersion;
S3、将75份TPU置于20份酒精溶液中，然后在95℃进行搅拌，溶解完全；S3. Put 75 parts of TPU in 20 parts of alcohol solution, and then stir at 95°C to dissolve completely;
S4、将步骤S2的多孔石墨烯分散液与步骤S3的TPU溶液混合，再加入0.4份光稳定剂，搅拌均匀后，在0.07MPa下脱泡35min，将脱泡后的混合溶液通过涂布的方式均匀涂布在离型纸上，然后将涂布后的离型纸送入烘箱中进行烘干干燥，将干燥后的产品常温固化，完全固化后即可得到防水透气TPU热熔胶膜。S4. Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, then add 0.4 parts of light stabilizer, stir evenly, defoam at 0.07MPa for 35 minutes, evenly coat the degassed mixed solution on the release paper by coating, then send the coated release paper into an oven for drying and drying, and cure the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot melt adhesive film can be obtained.
实施例3Example 3
一种防水透气TPU热熔胶膜的制备方法，包括如下步骤：A preparation method of a waterproof and breathable TPU hot-melt adhesive film, comprising the steps of:
S1、将45份氧化石墨烯分散在水中，然后加入过氧化氢溶液，115℃反应5h，反应完成后加入1份还原剂继续反应3.5h后离心或过滤收集固体产物，得到多孔石墨烯；S1. Disperse 45 parts of graphene oxide in water, then add hydrogen peroxide solution, and react at 115°C for 5 hours. After the reaction is completed, add 1 part of reducing agent to continue the reaction for 3.5 hours, then centrifuge or filter to collect the solid product to obtain porous graphene;
S2、将步骤S1中的多孔石墨烯分散在酒精溶液中，然后加入1.5份疏水剂，反应40min后，加入2份致孔剂，搅拌均匀得到改性多孔石墨烯分散液；S2, disperse the porous graphene in the step S1 in the alcohol solution, then add 1.5 parts of hydrophobic agents, after reacting for 40min, add 2 parts of porogens, stir to obtain the modified porous graphene dispersion;
S3、将80份TPU置于25份酒精溶液中，然后在100℃进行搅拌，溶解完全；S3. Put 80 parts of TPU in 25 parts of alcohol solution, and then stir at 100°C to dissolve completely;
S4、将步骤S2的多孔石墨烯分散液与步骤S3的TPU溶液混合，再加入0.3份光稳定剂，搅拌均匀后，在0.1MPa下脱泡45min，将脱泡后的混合溶液通过涂布的方式均匀涂布在离型纸上，然后将涂布后的离型纸送入烘箱中进行烘干干燥，将干燥后的产品常温固化，完全固化后即可得到防水透气TPU热熔胶膜。S4. Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, then add 0.3 parts of light stabilizer, stir evenly, defoam at 0.1 MPa for 45 minutes, evenly coat the degassed mixed solution on the release paper by coating, then send the coated release paper into an oven for drying, and dry the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot-melt adhesive film can be obtained.
对比例1Comparative example 1
本对比例的的原料组成及重量份如下：致孔剂为0份；The raw material composition and parts by weight of this comparative example are as follows: porogen is 0 part;
制备方法同实施例1。The preparation method is the same as in Example 1.
对比例2Comparative example 2
本对比例的的原料组成及重量份如下：氧化石墨烯和致孔剂均为0份；The raw material composition and parts by weight of this comparative example are as follows: graphene oxide and porogen are 0 parts;
制备方法同实施例2。The preparation method is the same as in Example 2.
对实施例1-3和对比例1-2制备的TPU薄膜进行水蒸气透过率测试、耐水压测试以及抗张强度测试。其中，水蒸气透过率测试采用GB/T 1037-1988中所述的方法以及性能参数，测试结果如下表所示：The TPU films prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to a water vapor transmission rate test, a water pressure resistance test and a tensile strength test. Among them, the water vapor transmission rate test adopts the method and performance parameters described in GB/T 1037-1988, and the test results are shown in the following table:
 the 水蒸气透过率(g/m 2·24h) Water vapor transmission rate (g/m 2 ·24h) 静水压/mHydrostatic pressure/m 抗张强度/MPaTensile strength/MPa
实施例1Example 1 14913.214913.2 4.74.7 20.220.2
实施例2Example 2 15019.615019.6 4.94.9 21.821.8
实施例3Example 3 17579.117579.1 4.44.4 22.122.1
对比例1Comparative example 1 9243.29243.2 3.63.6 19.219.2
对比例2Comparative example 2 8987.88987.8 3.03.0 17.417.4
上述说明示出并描述了本发明的优选实施例，如前所述，应当理解本发明并非局限于本文所披露的形式，不应看作是对其他实施例的排除，而可用于各种其他组合、修改和环境，并能够在本文所述发明构想范围内，通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围，则都应在本发明所附权利要求的保护范围内。The above description shows and describes the preferred embodiments of the present invention. As mentioned above, it should be understood that the present invention is not limited to the forms disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the inventive concept described herein, through the above teachings or technology or knowledge in related fields. However, changes and changes made by those skilled in the art do not depart from the spirit and scope of the present invention, and should all be within the protection scope of the appended claims of the present invention.

Claims (10)

  1. 一种防水透气TPU热熔胶膜，其特征在于，包括如下重量份数的组分：A waterproof and breathable TPU hot melt adhesive film, characterized in that it comprises the following components in parts by weight:
    Figure PCTCN2022074643-appb-100001
    Figure PCTCN2022074643-appb-100001
  2. 根据权利要求1所述的防水透气TPU热熔胶膜，其特征在于，所述溶剂的浓度为0.6～0.9mol/L。The waterproof and breathable TPU hot melt adhesive film according to claim 1, characterized in that the concentration of the solvent is 0.6-0.9 mol/L.
  3. 根据权利要求1所述的防水透气TPU热熔胶膜，其特征在于，所述氧化石墨烯的浓度为21～25mg/mL。The waterproof and breathable TPU hot-melt adhesive film according to claim 1, wherein the concentration of the graphene oxide is 21-25 mg/mL.
  4. 根据权利要求1所述的防水透气TPU热熔胶膜，其特征在于，所述致孔剂为聚乙烯吡咯烷酮、聚乙二醇中的至少一种。The waterproof and breathable TPU hot-melt adhesive film according to claim 1, wherein the porogen is at least one of polyvinylpyrrolidone and polyethylene glycol.
  5. 根据权利要求1所述的防水透气TPU热熔胶膜，其特征在于，所述疏水剂为聚四氟乙烯、聚三氟氯乙烯、聚全氟乙丙烯中的一种或几种。The waterproof and breathable TPU hot-melt adhesive film according to claim 1, wherein the hydrophobic agent is one or more of polytetrafluoroethylene, polychlorotrifluoroethylene, and polyperfluoroethylene propylene.
  6. 根据权利要求1所述的防水透气TPU热熔胶膜，其特征在于，所述还原剂为葡萄糖、二甲基胺硼烷中的一种或两种。The waterproof and breathable TPU hot-melt adhesive film according to claim 1, wherein the reducing agent is one or both of glucose and dimethylamine borane.
  7. 根据权利要求1所述的防水透气TPU热熔胶膜，其特征在于，所述光稳定剂为癸二酸二(2,2,6,6-四甲基-4-哌啶)酯、聚[[6-[(1,1,3,3-四甲基丁基)胺]-1,3,5-三嗪-2,4-二基][(2,2,6,6-四甲基-4-哌啶)亚胺]-1,6-二己二基[(2,2,6,6-四甲基-4-哌啶)亚胺]]]、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯中的任意一种或至少两种的混合物。The waterproof and breathable TPU hot-melt adhesive film according to claim 1, wherein the light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidine) sebacate, poly[[6-[(1,1,3,3-tetramethylbutyl)amine]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidine)imine]-1,6-dihexanediyl[(2,2, Any one of 6,6-tetramethyl-4-piperidinyl)imine]]], bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate or a mixture of at least two.
  8. 一种防水透气TPU热熔胶膜的制备方法，其特征在于，包括如下步骤：A kind of preparation method of waterproof breathable TPU hot-melt adhesive film is characterized in that, comprises the steps:
    S1、将氧化石墨烯分散在水中，然后加入过氧化氢溶液，110～120℃反应1h～8h，反应完成后加入还原剂继续反应3～4h后离心或过滤收集固体产物，得到多孔石墨烯；S1. Disperse graphene oxide in water, then add hydrogen peroxide solution, and react at 110-120°C for 1h-8h. After the reaction is completed, add a reducing agent to continue the reaction for 3-4h, then centrifuge or filter to collect the solid product to obtain porous graphene;
    S2、将步骤S1中的多孔石墨烯分散在溶剂中，然后加入疏水剂，反应30～60min后，加入适量的致孔剂，搅拌均匀得到改性多孔石墨烯分散液；S2, dispersing the porous graphene in step S1 in a solvent, then adding a hydrophobic agent, after reacting for 30 to 60 minutes, adding an appropriate amount of porogen, and stirring evenly to obtain a modified porous graphene dispersion;
    S3、将TPU置于溶剂中，然后在95～100℃进行搅拌，溶解完全；S3. Put the TPU in the solvent, and then stir at 95-100°C to dissolve completely;
    S4、将步骤S2的多孔石墨烯分散液与步骤S3的TPU溶液混合，再加入光稳定剂，搅拌均匀后，在0.07～0.1MPa下脱泡35～50min，将脱泡后的混合溶液通过涂布的方式均匀涂布在离型纸上，然后将涂布后的离型纸送入烘箱中进行烘干干燥，将干燥后的产品常温固化，完全固化后即可得到防水透气TPU热熔胶膜。S4. Mix the porous graphene dispersion in step S2 with the TPU solution in step S3, add a light stabilizer, stir evenly, and defoam at 0.07 to 0.1 MPa for 35 to 50 minutes. Apply the defoamed mixed solution evenly on the release paper by coating, then send the coated release paper into an oven for drying and drying, and cure the dried product at room temperature. After complete curing, a waterproof and breathable TPU hot melt adhesive film can be obtained.
  9. 根据权利要求8所述的防水透气TPU热熔胶膜的制备方法，其特征在于，在所述步骤S4中，所述涂布的间隙为0.6-1mm。The method for preparing a waterproof and breathable TPU hot-melt adhesive film according to claim 8, characterized in that, in the step S4, the coating gap is 0.6-1 mm.
  10. 根据权利要求8所述的防水透气TPU热熔胶膜的制备方法，其特征在于，在所述步骤S4中，所述烘箱的温度设为130-150℃。The method for preparing a waterproof and breathable TPU hot-melt adhesive film according to claim 8, characterized in that, in the step S4, the temperature of the oven is set at 130-150°C.
PCT/CN2022/074643 2022-01-21 2022-01-28 Waterproof gas-permeable tpu hot-melt adhesive film and preparation process therefor WO2023137791A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210073658.X 2022-01-21
CN202210073658.XA CN114479683A (en) 2022-01-21 2022-01-21 Waterproof and breathable TPU (thermoplastic polyurethane) hot melt adhesive film and preparation process thereof

Publications (1)

Publication Number Publication Date
WO2023137791A1 true WO2023137791A1 (en) 2023-07-27

Family

ID=81472414

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/074643 WO2023137791A1 (en) 2022-01-21 2022-01-28 Waterproof gas-permeable tpu hot-melt adhesive film and preparation process therefor

Country Status (2)

Country Link
CN (1) CN114479683A (en)
WO (1) WO2023137791A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114989732A (en) * 2022-05-17 2022-09-02 广东汇齐新材料有限公司 Preparation method of waterproof and moisture permeable TPU hot melt adhesive film

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104263259A (en) * 2014-09-18 2015-01-07 东莞市雄林新材料科技股份有限公司 Low-melting-point and high-bonding-strength TPU (thermoplastic polyurethane) hot melt adhesive membrane and preparation method thereof
CN107488268A (en) * 2017-09-15 2017-12-19 重庆石墨烯研究院有限公司 Polyurethane porous film of graphene-containing and its production and use
WO2018215386A1 (en) * 2017-05-24 2018-11-29 Solvay Specialty Polymers Italy S.P.A. Monolithic breathable membrane
CN108929457A (en) * 2018-06-25 2018-12-04 董小琳 A kind of TPU waterproof ventilated membrane and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108641662B (en) * 2018-05-11 2020-12-11 美瑞新材料股份有限公司 Low-softening-point waterproof moisture-permeable TPU hot melt adhesive and preparation method thereof
CN113578656A (en) * 2021-07-09 2021-11-02 江苏惠沣环保科技有限公司 Preparation method of TPU (thermoplastic polyurethane) hot melt adhesive film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104263259A (en) * 2014-09-18 2015-01-07 东莞市雄林新材料科技股份有限公司 Low-melting-point and high-bonding-strength TPU (thermoplastic polyurethane) hot melt adhesive membrane and preparation method thereof
WO2018215386A1 (en) * 2017-05-24 2018-11-29 Solvay Specialty Polymers Italy S.P.A. Monolithic breathable membrane
CN107488268A (en) * 2017-09-15 2017-12-19 重庆石墨烯研究院有限公司 Polyurethane porous film of graphene-containing and its production and use
CN108929457A (en) * 2018-06-25 2018-12-04 董小琳 A kind of TPU waterproof ventilated membrane and preparation method thereof

Also Published As

Publication number Publication date
CN114479683A (en) 2022-05-13

Similar Documents

Publication Publication Date Title
WO2023137791A1 (en) Waterproof gas-permeable tpu hot-melt adhesive film and preparation process therefor
CN110330782B (en) Preparation method of modified graphene oxide/polyurethane heat-resistant composite material
US20160362577A1 (en) A waterproof and oxygen-isolating sealing film and preparation method
WO2022057467A1 (en) Modified collagen fiber and use thereof
CN105879704A (en) Preparation method and application of mixed matrix membrane containing zeolite imidazolate framework material
WO2018036426A1 (en) Modified nanometer composite polysulfide sealant for fireproof glass and preparation method therefor
CN108283889A (en) A kind of composite membrane, preparation method and the application in gas separation, purifying
CN114716624A (en) Modified polyacrylate flame-retardant emulsion, modified polyacrylate flame-retardant pressure-sensitive adhesive containing emulsion and preparation method of modified polyacrylate flame-retardant pressure-sensitive adhesive
JPS5924845B2 (en) Method for manufacturing gas selective permeability composite membrane
WO2021037273A1 (en) Covalent organic frame flame retardant having schiff base-containing vanillin group, and preparation method therefor
CN111004602B (en) UV (ultraviolet) photocuring adhesive and double-sided adhesive tape prepared by using same
CN106883664B (en) Benzene-series pollutant remover and preparation method thereof
CN106046618B (en) A kind of application of two pyridine ester of phosphorous acid in PVC heat stabilizer
CN104878130A (en) Complex-function amino resin tanning agent and preparation method thereof
CN108059600A (en) One kind four（Dimethylamino）The process for purification of titanium
JPS588506A (en) Selective separation membrane
CN109337110A (en) Waterproof ventilated membrane and preparation method thereof
CN115678574A (en) Single-component intumescent flame retardant and preparation method and application thereof
CN111138657B (en) Terpolymer resin
CN112063358A (en) Processing method for improving bonding strength of wooden artware
CN112375267A (en) Modified zinc oxide/rubber composite material and preparation method thereof
CN111592844A (en) Hot-melt pressure-sensitive adhesive for high-temperature adhesive tape and preparation method thereof
CN104532578A (en) Polytetrafluoroethylene glass fiber breathable varnished cloth and formula
CN112538185A (en) Preparation method of polylactic acid gas barrier composite membrane
CN108395703B (en) Mesoporous material-based intumescent flame-retardant silicone rubber and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22921227

Country of ref document: EP

Kind code of ref document: A1